EP0249289B1 - Verfahren zur Herstellung von Chinonen - Google Patents

Verfahren zur Herstellung von Chinonen Download PDF

Info

Publication number
EP0249289B1
EP0249289B1 EP87201075A EP87201075A EP0249289B1 EP 0249289 B1 EP0249289 B1 EP 0249289B1 EP 87201075 A EP87201075 A EP 87201075A EP 87201075 A EP87201075 A EP 87201075A EP 0249289 B1 EP0249289 B1 EP 0249289B1
Authority
EP
European Patent Office
Prior art keywords
process according
hydrogen
phenol
comprised
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP87201075A
Other languages
English (en)
French (fr)
Other versions
EP0249289A2 (de
EP0249289A3 (en
Inventor
Francesco Minisci
Attilio Citterio
Elena Vismara
Sivia De Bernardinis
Carlo Neri
Luciano Pallini
Mariano Correale
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Enichem Sintesi SpA
Consiglio Nazionale delle Richerche CNR
Original Assignee
Brichima SpA
Enichem Sintesi SpA
Consiglio Nazionale delle Richerche CNR
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Brichima SpA, Enichem Sintesi SpA, Consiglio Nazionale delle Richerche CNR filed Critical Brichima SpA
Priority to AT87201075T priority Critical patent/ATE68465T1/de
Publication of EP0249289A2 publication Critical patent/EP0249289A2/de
Publication of EP0249289A3 publication Critical patent/EP0249289A3/en
Application granted granted Critical
Publication of EP0249289B1 publication Critical patent/EP0249289B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
    • C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring

Definitions

  • the object of the present invention is a novel catalytic process for the synthesis of quinones. Such process is accomplished by oxidating 2,6-disubstituted phenols or diphenols with H2O2 in the presence of catalytic amounts of bromine, iodine, hydrogen bromide, or hydrogen iodide: the catalytic oxidation which is thus accomplished is extremely simple, cheap and highly selective.
  • Quinones are known to be an important class of compounds of the chemical industry; thus, 1,4-benzoquinone is used in the photographic industry and in the industry of the dyes; 1,4-naphthoquinone and 9.10-anthraquinone is used in the industry of dyes, 2-methylnaphthoquinone is a commercial Vitamin K, and 2,3,5-trimethyl-1,4-benzoquinone is an intermediate for the synthesis of vitamins, etc. (D.H. Barton "Comprehensive Organic Chemistry", Vol. 1, page 1,213, 1979).
  • quinones can be easily hydrogenated to yield diphenols
  • compounds which too are industrially useful, in particular in the photographic fields, and in the field of antioxidants these latter may be conveniently obtained by starting from quinones, which are obtained, in their turn, by starting from mono-phenols, whenever these latter are easily accessible products.
  • a general method for the synthesis of quinones is constituted by the oxidation of phenols and diphenols with various oxidants, such as CrO3, Ag2O, Ag2CO3, Ce IV salts, the Fremy salt (KO3S)2NO, (PhSeO)2O and so forth.
  • oxidants such as CrO3, Ag2O, Ag2CO3, Ce IV salts, the Fremy salt (KO3S)2NO, (PhSeO)2O and so forth.
  • the use of these oxidants shows serious drawbacks from the industrial viewpoint, such as, e.g., not compatible costs (this is the case of the salts of Ag, Ce, of the Fremy salt, of selenium derivatives, etc.), or large amounts of salts to be disposed of (chrome salts), or highly toxic substances (selenium oxides).
  • a method is known as well for the oxidation of phenols to quinones, which uses hydrogen peroxide, but which is carried out in two steps, and provides first the synthesis of the analogous 4-chloro derivative, by means of the treatment of the phenol with HCl and H2O2 followed, in a second step, by the oxidation of this intermediate with H2O2 in acetic acid, to yield the quinone (see C.A. 85 , 94070c).
  • R represents hydrogen, alkyl, alkoxy, aryl, halogen or hydroxy
  • R1 is hydrogen or alkyl
  • R2 can be hydrogen or
  • alkyl means a straight or branched chain alkyl radical containing from 1 to 6 carbon atoms, such as, e.g., methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, tert.butyl, pentyl, hexyl, etc. and, analogously, the term “alkoxy” identifies a straight or branched chain alkoxy radical containing from 1 to 6 carbon atoms, such as, e.g., methoxy, ethoxy, isopropoxy, tert.butoxy, pentyloxy etc..
  • aryl indicates a phenyl radical, or a phenyl radical substituted with one or more groups independently selected from alkyl, alkoxy and halogen.
  • halogen indicates any of chlorine, bromine, iodine and fluorine.
  • the process according to the present invention consists essentially in oxidating the phenol with H2O2 in the presence of a catalyst selected from bromine, iodine, hydrogen bromide and hydrogen iodide.
  • the reaction is preferably carried out by using commercial aqueous solutions of H2O2.
  • Suitable solvents for the intended purpose are all of the water-miscible organic solvents which are capable of dissolving the phenol, and do not interfere negatively with the course of the oxidation reaction, such as, e.g., the lower alkanols, typically methanol and ethanol, the organic acids, e.g., acetic acid, acetonitrile, etc..
  • the molar ratio between H2O2 and the phenol is preferably higher than 2, and still more preferably it is comprised within the range of from 2 to 3, whilst when diphenols are oxidated, such ratio is preferably comprised within the range of from 1 to 2, and still more preferably within the range of from 1 to 1.5. Higher molar ratios can be used, but they do not afford any further advantages for the same reaction.
  • the reaction is carried out at a temperature generally comprised within the range of from 0°C to the refluxing temperature of the reaction mixture and preferably, when mono-phenols are oxidated, at a temperature comprised within the range of from room temperature to the refluxing temperature of the reaction mixture, and, when the diphenols are oxidated, within the range of from 0°C to 60°C.
  • This situation can be accomplished both by reacting all of the reactants together and using a catalyst amount equal to at least 51% of the starting phenol, and, more conveniently, using a much lower catalyst amount, but adding, gradually over time, the phenol to the solution of the catalyst and hydrogen peroxide, in such a way that the steady-state concentration of the catalyst is always higher than 50% of the steady-state concentration of the phenol, due to the fact that the phenol reacts rapidly, and its concentration in the reaction medium remains always low, whilst the concentration of the catalyst remains substantially equal to its initial concentration.
  • the reaction rate can be increased, is desired, by initially adding a strong acid, which can be the same hydrogen bromide or hydrogen iodide, but which can also be sulphuric acid. This addition does not alter the very good selectivity of the process, but simply makes it faster.
  • a strong acid which can be the same hydrogen bromide or hydrogen iodide, but which can also be sulphuric acid.
  • This addition does not alter the very good selectivity of the process, but simply makes it faster.
  • the product is easily separated from the solution by crystallization, after possibly preliminarily removing a portion of the solvent.
  • the process of the present invention leads to the corresponding quinone with high yields and with a high selectivity.
  • reaction mixture is refluxed for further 5 minutes, the solution is concentrated to small volume (50 ml) and 2,6-di-tert.butyl-1,4-benzoquinone (10.6 g, 90.4%) is crystallized.
  • a solution of a suitable diphenol (20 mmol) in methanol or acetic acid (60 ml) is treated 4 hours long with hydrogen peroxide at 60% (22 mmol), concentrated sulphuric acid (1 ml) and bromine or iodine or hydrogen iodide (1 mmol) at 25°C.
  • Trimethyl-benzoquinone separates initially in an oily state, but solidifies after cooling.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Meat, Egg Or Seafood Products (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Fodder In General (AREA)

Claims (23)

  1. Verfahren zur Synthese von Chinonen durch Oxidation von 2,6-disubstituierten Monophenolen oder von Diphenolen, dadurch gekennzeichnet, daß die Oxidation mit Wasserstoffperoxid in Gegenwart katalytischer Mengen eines unter Brom, Iod, Bromwasserstoff und Iodwasserstoff ausgewählten Mittels ausgeführt wird.
  2. Verfahren nach Anspruch 1, worin die Phenol-Ausgangsprodukte Verbindungen mit der allgemeinen Formel (I):
    Figure imgb0007
     sind, worin
    R   für Wasserstoff, Alkyl, Alkoxy, Aryl, Halogen oder Hydroxy steht,
    R₁   Wasserstoff oder Alkyl bedeutet,
    R₂   Wasserstoff oder Hydroxy sein kann,
    R₃   Wasserstoff oder Alkyl ist,
    R₄   für Wasserstoff, Alkyl, Alkoxy, Aryl oder Halogen steht oder
    R und R₁ und/oder R₃ und R₄,   zusammengenommen, eine Butadienylkette der Formel



            -CH=CH-CH=CH-



    bedeuten, die an dem Phenol einen kondensierten Ring ausbildet, mit der Maßgabe, daß R nur dann ein Wasserstoffatom bedeuten kann, wenn R₂ Hydroxy darstellt, und mit der weiteren Maßgabe, daß R₄ nur dann Wasserstoff bedeuten kann, wenn einer der Reste von R und R₂ für Hydroxysteht.
  3. Verfahren nach Anspruch 1, worin Wasserstoffperoxid in wäßriger Lösung verwendet wird.
  4. Verfahren nach Anspruch 3, worin die Umsetzung in Gegenwart eines zum Auflösen des Phenolausgangsproduktes befähigten Lösungsmittels ausgeführt wird, das mit Wasser mischbar ist und den Ablauf der Reaktion nicht nachteilig beeinflußt.
  5. Verfahren nach Anspruch 4, worin das Lösungsmittel unter niederen Alkanolen und organischen Säuren ausgewählt wird.
  6. Verfahren nach Anspruch 5, worin das Lösungsmittel unter Methanol, Ethanol und Essigsäure ausgewählt wird.
  7. Verfahren nach Anspruch 1, worin die Umsetzung bei einer Temperatur im Bereich von 0°C bis zur Rückflußtemperatur des Reaktionsgemisches ausgeführt wird.
  8. Verfahren nach Anspruch 1, worin das Phenolausgangsprodukt ein 2,6-disubstituiertes Monophenol ist.
  9. Verfahren nach Anspruch 8, worin der Katalysator unter Brom und Bromwasserstoff ausgewählt wird.
  10. Verfahren nach Anspruch 9, worin der Katalysator Brom ist.
  11. Verfahren nach Anspruch 8, worin das Wasserstoffperoxid in einer solchen Menge verwendet wird, daß das Molverhältnis von Wasserstoffperoxid zu Phenolausgangsprodukt größer als 2 ist.
  12. Verfahren nach Anspruch 11, worin das Verhältnis im Bereich von 2 bis 3 liegt.
  13. Verfahren nach Anspruch 8, worin während des Reaktionsablaufes die Molkonzentration des Katalysators höher als 50% der Gleichgewichtskkonzentration des Phenols liegt.
  14. Verfahren nach Anspruch 8, worin die Temperatur im Bereich von Raumtemperatur bis zur Rückflußtemperatur des Reaktionsgemisches liegt.
  15. Verfahren nach Anspruch 1, worin das Phenolausgangsprodukt ein Diphenol ist.
  16. Verfahren nach Anspruch 15, worin der Katalysator unter Iod und Iodwasserstoff ausgewählt wird.
  17. Verfahren nach Anspruch 16, worin der Katalysator Iod ist.
  18. Verfahren nach Anspruch 15, worin das Wasserstoffperoxid in einer solchen Menge eingesetzt wird, daß das Molverhältnis von Wasserstoffperoxid zu dem Phenolausgangsprodukt im Bereich von 1 bis 2 liegt.
  19. Verfahren nach Anspruch 18, worin das Verhältnis im Bereich 1 bis 1,5 liegt.
  20. Verfahren nach Anspruch 15, worin der Katalysator in einer Menge im Bereich von 0,1 bis 10 Mol-%, bezogen auf das als Ausgangsprodukt verwendete Diphenol, eingesetzt wird.
  21. Verfahren nach Anspruch 15, worin die Temperatur im Bereich von 0°C bis 60°C gehalten wird.
  22. Verfahren nach Anspruch 1, worin die Umsetzung in Gegenwart einer starken Säure ausgeführt wird.
  23. Verfahren nach Anspruch 22, worin die starke Säure Schwefelsäure ist.
EP87201075A 1986-06-11 1987-06-09 Verfahren zur Herstellung von Chinonen Expired - Lifetime EP0249289B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87201075T ATE68465T1 (de) 1986-06-11 1987-06-09 Verfahren zur herstellung von chinonen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT20754/86A IT1191803B (it) 1986-06-11 1986-06-11 Procedimento per la preparazione di chinoni
IT2075486 1986-06-11

Publications (3)

Publication Number Publication Date
EP0249289A2 EP0249289A2 (de) 1987-12-16
EP0249289A3 EP0249289A3 (en) 1988-12-14
EP0249289B1 true EP0249289B1 (de) 1991-10-16

Family

ID=11171561

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87201075A Expired - Lifetime EP0249289B1 (de) 1986-06-11 1987-06-09 Verfahren zur Herstellung von Chinonen

Country Status (6)

Country Link
EP (1) EP0249289B1 (de)
AT (1) ATE68465T1 (de)
DE (1) DE3773750D1 (de)
ES (1) ES2028050T3 (de)
GR (1) GR3003208T3 (de)
IT (1) IT1191803B (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01102042A (ja) * 1987-10-16 1989-04-19 Sanko Kaihatsu Kagaku Kenkyusho:Kk ｐ−ベンゾキノンの製造方法
ES3023519T3 (en) * 2021-05-07 2025-06-02 Ivoclar Vivadent Ag Transparent, fracture-resistant polymerisation resins for the production of dental mouldings

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297445A (en) * 1963-04-01 1967-01-10 Eastman Kodak Co Photographic inhibitor releasing developers
DE2460361A1 (de) * 1974-12-20 1976-06-24 Merck Patent Gmbh Verfahren zur herstellung von trimethylchinonen

Also Published As

Publication number Publication date
GR3003208T3 (en) 1993-02-17
IT8620754A0 (it) 1986-06-11
IT1191803B (it) 1988-03-23
ATE68465T1 (de) 1991-11-15
ES2028050T3 (es) 1992-07-01
EP0249289A2 (de) 1987-12-16
EP0249289A3 (en) 1988-12-14
IT8620754A1 (it) 1987-12-11
DE3773750D1 (de) 1991-11-21

Similar Documents

Publication Publication Date Title
Fetizon et al. Oxidations with silver carbonate/celite. V. Oxidations of phenols and related compounds
KR100395987B1 (ko) 알릴에테르,알릴티오에테르및알릴아민화합물의제조방법
JPS6230122B2 (de)
Omura Oxidation of phenols with iodine in alkaline methanol
US3247262A (en) Process for making polyphenols
US4108908A (en) Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of thio-acid compounds
US4100205A (en) Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of aminoketo compounds
US4139544A (en) Oxidative coupling of alkylphenols catalyzed by metal complexes of polyimino acids
EP0249289B1 (de) Verfahren zur Herstellung von Chinonen
US4101561A (en) Oxidative coupling of alkylphenols catalyzed by metal complexes of imino acid compounds
US5175318A (en) Process for the preparation of quinones
Nishino et al. Choice of Manganese (III) Complexes for the Synthesis of 4, 4'-Biphenyldiols and 4, 4'-Diphenoquiones.
CN113735696A (zh) 一种醌类化合物的制备方法
EP0058057B1 (de) Verfahren zur Herstellung von Chinonderivaten
US4772754A (en) Process for the isolation of p-hydroxybenzaldehyde
IL45113A (en) 6-substituted-2-benzoxyzolinone derivatives and their preparation
US4098830A (en) Oxidative coupling of alkylphenols or 1-naphthols catalyzed by metal complexes of dicarboxylic acid compounds
EP0011296B1 (de) Oxidatives Verfahren zur Herstellung von substituierten Biphenolen
US4086253A (en) 3,3',5,5'-Tetra-substituted diphenoquinone from 2,6-disubstituted phenol by phase-transfer catalysis
CA1192915A (en) Production of hydroquinone
EP0167153B1 (de) Verfahren zur Herstellung von 2,3,5-Trimethylbenzochinon
US3833660A (en) Process for making aromatic aldehydes
EP0445483B1 (de) Katalytische Oxydation von Hydroxygruppen enthaltende aromatische Verbindungen
US5545760A (en) Process for making fluorenones
US3966776A (en) Process for preparing parabenzoquinones

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE ES FR GB GR LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE ES FR GB GR LI LU NL SE

17P Request for examination filed

Effective date: 19890308

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ENICHEM SYNTHESIS S.P.A.

Owner name: CONSIGLIO NAZIONALE DELLE RICERCHE

17Q First examination report despatched

Effective date: 19901212

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR LI LU NL SE

REF Corresponds to:

Ref document number: 68465

Country of ref document: AT

Date of ref document: 19911115

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3773750

Country of ref document: DE

Date of ref document: 19911121

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2028050

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3003208

EPTA Lu: last paid annual fee
EAL Se: european patent in force in sweden

Ref document number: 87201075.6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20010417

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20010605

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20010606

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20010611

Year of fee payment: 15

Ref country code: FR

Payment date: 20010611

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20010613

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20010615

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20010627

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20010628

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20010629

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20010816

Year of fee payment: 15

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020609

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020609

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020609

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020610

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020610

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020630

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020630

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020630

BERE Be: lapsed

Owner name: *ENICHEM SYNTHESIS S.P.A.

Effective date: 20020630

Owner name: *CONSIGLIO NAZIONALE DELLE RICERCHE

Effective date: 20020630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20021231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030101

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020609

EUG Se: european patent has lapsed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030228

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20030101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20030711